Global Elemental Cycles Research Articles

Overview of the mechanisms that could explain the 'Boundary Exchange' at the land-ocean contact.

Land to ocean transfer of material largely controls the chemical composition of seawater and the global element cycles. Oceanic isotopic budgets of chemical species, macro- and micronutrients (e.g. Nd, Sr, Si, Mg, Zn, Mo and Ni) have revealed an imbalance between their sources and sinks. Radiogenic isotope budgets underlined the importance of taking into account continental margins as a source of elements to oceans. They also highlighted that the net land-ocean inputs of chemical species probably result from particle-dissolved exchange processes, named 'Boundary Exchange'. Yet, locations where 'Boundary Exchange' occurs are not clearly identified and reviewed here: discharge of huge amount of freshly weathered particles at the river mouths, submarine weathering of deposited sediments along the margins, submarine groundwater discharges and subterranean estuaries. As a whole, we conclude that all of them might contribute to 'Boundary Exchange'. Highlighting their specific roles and the processes at play is a key scientific issue for the second half of GEOTRACES.This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'.

Comprehensive structure-selective characterization of dissolved organic matter by reducing molecular complexity and increasing analytical dimensions

Deciphering the molecular codes of dissolved organic matter (DOM) improves our understanding of its role in the global element cycles and its active involvement in ecosystem services. This study demonstrates comprehensive characterization of DOM by an initial polarity-based stepwise solid phase extraction (SPE) with single methanol elution of the cartridges, but separate collection of equal aliquots of eluate. The reduction of molecular complexity in the individual DOM fractions attenuates intermolecular interactions and substantially increases the disposable resolution of any structure selective characterization. Suwannee River DOM (SR DOM) was used to collect five distinct SPE fractions with overall 91% DOC recovery. Optical spectroscopy (UV and fluorescence spectroscopy), high-field Fourier transform ion cyclotron mass spectrometry (FTICR MS) and nuclear magnetic resonance (NMR) spectroscopy showed analogous hierarchical clustering among the five eluates corroborating the robustness of this approach. Two abundant moderately hydrophobic fractions contained most of the SR DOM compounds, with substantial proportions of aliphatics, carboxylic-rich alicyclic molecules, carbohydrates and aromatics. A minor early eluting hydrophilic fraction was highly aliphatic and presented a large diversity of alicyclic carboxylic acids, whereas the two late eluting, minor hydrophobic fractions appeared as a largely defunctionalized mixture of aliphatic molecules. Comparative mass analysis showed that fractionation of SR DOM was governed by multiple molecular interactions depending on O/C ratio, molecular weight and aromaticity. The traditional optical indices SUVA254 and fluorescence index (FI) indicated the relative aromaticity in agreement with FTICR mass and NMR spectra; the classical fluorescent peaks A and C were observed in all four latter eluates. This versatile approach can be easily expanded to preparative scale under field conditions, and transferred to different DOM sources and SPE conditions.

Combined genomic and structural analyses of a cultured magnetotactic bacterium reveals its niche adaptation to a dynamic environment.

BackgroundMagnetotactic bacteria (MTB) are a unique group of prokaryotes that have a potentially high impact on global geochemical cycling of significant primary elements because of their metabolic plasticity and the ability to biomineralize iron-rich magnetic particles called magnetosomes. Understanding the genetic composition of the few cultivated MTB along with the unique morphological features of this group of bacteria may provide an important framework for discerning their potential biogeochemical roles in natural environments.ResultsGenomic and ultrastructural analyses were combined to characterize the cultivated magnetotactic coccus Magnetofaba australis strain IT-1. Cells of this species synthesize a single chain of elongated, cuboctahedral magnetite (Fe3O4) magnetosomes that cause them to align along magnetic field lines while they swim being propelled by two bundles of flagella at velocities up to 300 μm s−1. High-speed microscopy imaging showed the cells move in a straight line rather than in the helical trajectory described for other magnetotactic cocci. Specific genes within the genome of Mf. australis strain IT-1 suggest the strain is capable of nitrogen fixation, sulfur reduction and oxidation, synthesis of intracellular polyphosphate granules and transporting iron with low and high affinity. Mf. australis strain IT-1 and Magnetococcus marinus strain MC-1 are closely related phylogenetically although similarity values between their homologous proteins are not very high.Conclusion Mf. australis strain IT-1 inhabits a constantly changing environment and its complete genome sequence reveals a great metabolic plasticity to deal with these changes. Aside from its chemoautotrophic and chemoheterotrophic metabolism, genomic data indicate the cells are capable of nitrogen fixation, possess high and low affinity iron transporters, and might be capable of reducing and oxidizing a number of sulfur compounds. The relatively large number of genes encoding transporters as well as chemotaxis receptors in the genome of Mf. australis strain IT-1 combined with its rapid swimming velocities, indicate that cells respond rapidly to environmental changes.Electronic supplementary materialThe online version of this article (doi:10.1186/s12864-016-3064-9) contains supplementary material, which is available to authorized users.

Size and Carbon Content of Sub-seafloor Microbial Cells at Landsort Deep, Baltic Sea.

The discovery of a microbial ecosystem in ocean sediments has evoked interest in life under extreme energy limitation and its role in global element cycling. However, fundamental parameters such as the size and the amount of biomass of sub-seafloor microbial cells are poorly constrained. Here we determined the volume and the carbon content of microbial cells from a marine sediment drill core retrieved by the Integrated Ocean Drilling Program (IODP), Expedition 347, at Landsort Deep, Baltic Sea. To determine their shape and volume, cells were separated from the sediment matrix by multi-layer density centrifugation and visualized via epifluorescence microscopy (FM) and scanning electron microscopy (SEM). Total cell-carbon was calculated from amino acid-carbon, which was analyzed by high-performance liquid chromatography (HPLC) after cells had been purified by fluorescence-activated cell sorting (FACS). The majority of microbial cells in the sediment have coccoid or slightly elongated morphology. From the sediment surface to the deepest investigated sample (~60 m below the seafloor), the cell volume of both coccoid and elongated cells decreased by an order of magnitude from ~0.05 to 0.005 μm3. The cell-specific carbon content was 19–31 fg C cell−1, which is at the lower end of previous estimates that were used for global estimates of microbial biomass. The cell-specific carbon density increased with sediment depth from about 200 to 1000 fg C μm−3, suggesting that cells decrease their water content and grow small cell sizes as adaptation to the long-term subsistence at very low energy availability in the deep biosphere. We present for the first time depth-related data on the cell volume and carbon content of sedimentary microbial cells buried down to 60 m below the seafloor. Our data enable estimates of volume- and biomass-specific cellular rates of energy metabolism in the deep biosphere and will improve global estimates of microbial biomass.

Microbe-microbe interactions trigger Mn(II)-oxidizing gene expression.

Manganese (Mn) is an important metal in geochemical cycles. Some microorganisms can oxidize Mn(II) to Mn oxides, which can, in turn, affect the global cycles of other elements by strong sorption and oxidation effects. Microbe-microbe interactions have important roles in a number of biological processes. However, how microbial interactions affect Mn(II) oxidation still remains unknown. Here, we investigated the interactions between two bacteria (Arthrobacter sp. and Sphingopyxis sp.) in a co-culture, which exhibited Mn(II)-oxidizing activity, although neither were able to oxidize Mn(II) in isolation. We demonstrated that the Mn(II)-oxidizing activity in co-culture was most likely induced via contact-dependent interactions. The expressed Mn(II)-oxidizing protein in the co-culture was purified and identified as a bilirubin oxidase belonging to strain Arthrobacter. Full sequencing of the bilirubin oxidase-encoding gene (boxA) was performed. The Mn(II)-oxidizing protein and the transcripts of boxA were detected in the co-culture, but not in either of the isolated cultures. This indicate that boxA was silent in Arthrobacter monoculture, and was activated in response to presence of Sphingopyxis in the co-culture. Further, transcriptomic analysis by RNA-Seq, extracellular superoxide detection and cell density quantification by flow cytometry indicate induction of boxA gene expression in Arthrobacter was co-incident with a stress response triggered by co-cultivation with Sphingopyxis. Our findings suggest the potential roles of microbial physiological responses to stress induced by other microbes in Mn(II) oxidation and extracellular superoxide production.

Queuing Models for Abstracting Interactions in Bacterial Communities

Microbial communities play a significant role in bioremediation, plant growth, human and animal digestion, global elemental cycles including the carbon-cycle, and water treatment. They are also posed to be the engines of renewable energy via microbial fuel cells, which can reverse the process of electrosynthesis. Microbial communication regulates many virulence mechanisms used by bacteria. Thus, it is of fundamental importance to understand interactions in microbial communities and to develop predictive tools that help control them, in order to aid the design of systems exploiting bacterial capabilities. This position paper explores how abstractions from communications, networking and information theory can play a role in understanding and modeling bacterial interactions. In particular, two forms of interactions in bacterial systems will be examined: electron transfer and quorum sensing . While the diffusion of chemical signals has been heavily studied, electron transfer occurring in living cells and its role in cell–cell interaction is less understood. Recent experimental observations open up new frontiers in the design of microbial systems based on electron transfer, which may coexist with the more well-known interaction strategies based on molecular diffusion. In quorum sensing, the concentration of certain signature chemical compounds emitted by the bacteria is used to estimate the bacterial population size, so as to activate collective behaviors. In this position paper, queuing models for electron transfer are summarized and adapted to provide new models for quorum sensing. These models are stochastic, and thus capture the inherent randomness exhibited by cell colonies in nature. It is shown that queuing models allow the characterization of the state of a single cell as a function of interactions with other cells and the environment, thus enabling the construction of an information theoretic framework, while being amenable to complexity reduction using methods based on statistical physics and wireless network design.

Multiheme Cytochromes and the Bacterial Nanowires of Shewanella oneidensis MR-1: Regulation, Structure, and Extracellular Electron Transport Mechanisms

Dissimilatory metal-reducing bacteria can extract free energy from their environment by performing electron transfer to solid-phase minerals outside the cell. This extracellular electron transport (EET) has important implications in global elemental cycles as well as renewable energy technologies. Among the pathways for EET, bacterial nanowires have received significant attention in the past decade due to their unique ability to mediate long-range electron transport to electron acceptors microns away from the cell surface. Here we report a comprehensive characterization of the composition, structure, and regulatory network that underlies bacterial nanowires from the metal-reducing bacterium Shewanella oneidensis MR-1. Using fluorescent and atomic force techniques, we find that the Shewanella nanowires are extensions of the outer membrane and periplasm that contain multiple multiheme cytochromes. The localization of decaheme cytochromes MtrC and OmcA supports a multistep redox hopping mechanism, allowing long-range electron transport along a membrane network of heme cofactors that line the nanowires. The electron flux resulting from such a mechanism strongly depends on the cytochrome density and topology. Using correlated electron cryo-tomography and in vivo fluorescent microscopy, we are gaining new insight into the localization patterns of cytochromes along nanowires as well as the morphology and the formation mechanism of these structures. Finally, we report our progress on understanding the underlying regulatory network, by testing targeted mutations and analyzing the transcriptome of Shewanella chemostat cultures as they encounter electron acceptor limitation and form nanowires. The transcriptional response includes an increase in the expression of multiheme cytochromes, heme synthesis enzymes, and cytochrome maturation proteins. Our findings on the regulation, ultrastructure and electron transport mechanism help shape a biophysical understanding of these redox-functionalized membrane and vesicular extensions as a microbial strategy for electron transport and energy distribution.

Evidence for Strain-Specific Exometabolomic Responses of the Coccolithophore Emiliania huxleyi to Grazing by the Dinoflagellate Oxyrrhis marina

The coccolithophore Emiliania huxleyi forms massive blooms and plays a critical role in global elemental cycles, sequestering significant amounts of atmospheric carbon dioxide on geological time scales via production of calcium carbonate coccoliths and emitting dimethyl sulfoniopropionate (DMSP) which has the potential for increasing atmospheric albedo. Because grazing in pelagic systems is a major top-down force structuring microbial communities, the influence of grazers on E. huxleyi populations has been of interest to researchers. Roles of DMSP (and related metabolites) in interactions between E. huxleyi and protist grazers have been investigated, however, little is known about the release of other metabolites that may influence, or be influenced by, such grazing interactions. We used high-resolution mass spectrometry in an untargeted approach to survey the suite of low molecular weight compounds released by four different E. huxleyi strains in response to grazing by the dinoflagellate Oxyrrhis marina. Overall, a strikingly small number of metabolites were detected from E. huxleyi and O. marina cells, but these were distinctly informative to construct metabolic footprints. At most, E. huxleyi strains shared 25% of released metabolites. Furthermore, there appeared to be no unified metabolic response in E. huxleyi strains to grazing; rather these responses were strain specific. Concentrations of several metabolites also positively correlated with grazer activities, including grazing, ingestion, and growth rates; however, no single metabolite responded uniformly across all strains of E. huxleyi tested. Regardless, grazing clearly transformed the constituents of dissolved organic matter produced by these marine microbes. This study addresses several technical challenges, and presents a platform to further study the influence of chemical cues in aquatic systems and demonstrates the impact of strain diversity and grazing on the complexity of dissolved organic matter in marine systems.

Element flux to the environment of the passively degassing crater lake-hosting Kawah Ijen volcano, Indonesia, and implications for estimates of the global volcanic flux

Abstract Volcanoes play an important role in the global cycling of elements by providing a pathway from the deep Earth to its surface. Here, we have constrained the flux to the environment for most elements of the periodic table for the passively degassing, crater lake-hosting Kawah Ijen volcano in the Indonesian arc. Our results indicate that emissions of Kawah Ijen are dominated by acid water outflow, especially for the ligands (Cl, F, Br), with active fumaroles contributing significant (semi)metals (e.g. Se, As, Sb, Hg), as well as C and S. The compositional signature of emissions from Kawah Ijen is similar to that of major volcanic emitters such as Etna, but element fluxes are smaller. This result provides the prerequisite foundation for extrapolating a small set of measured volcanic gas emissions to a global volcanic flux estimate. However, the aqueous flux (i.e. seepage of volcanic hydrothermal fluids and volcano-influenced groundwater) is at least as important in terms of element release, and the consideration of the gaseous flux alone thus represents a significant underestimate of the impact of volcanoes on their environment and the contribution of volcanic hydrothermal systems to global element cycling. Supplementary material: The full datasets of water and fumarole gas chemical analyses are available at https://doi.org/10.6084/m9.figshare.c.2134359

The global ocean microbiome.

The microbiome of the largest environment on Earth has been gradually revealing its secrets over four decades of study. Despite the dispersed nature of substrates and the transience of surfaces, marine microbes drive essential transformations in all global elemental cycles. Much has been learned about the microbes that carry out key biogeochemical processes, but there are still plenty of ambiguities about the factors important in regulating activity, including the role of microbial interactions. Identifying the molecular "currencies" exchanged within the microbial community will provide key information on microbiome function and its vulnerability to environmental change.

Arsenic stress after the Proterozoic glaciations.

Protection against arsenic damage in organisms positioned deep in the tree of life points to early evolutionary sensitization. Here, marine sedimentary records reveal a Proterozoic arsenic concentration patterned to glacial-interglacial ages. The low glacial and high interglacial sedimentary arsenic concentrations, suggest deteriorating habitable marine conditions may have coincided with atmospheric oxygen decline after ~2.1 billion years ago. A similar intensification of near continental margin sedimentary arsenic levels after the Cryogenian glaciations is also associated with amplified continental weathering. However, interpreted atmospheric oxygen increase at this time, suggests that the marine biosphere had widely adapted to the reorganization of global marine elemental cycles by glaciations. Such a glacially induced biogeochemical bridge would have produced physiologically robust communities that enabled increased oxygenation of the ocean-atmosphere system and the radiation of the complex Ediacaran-Cambrian life.

Rising flux of nutrients (C, N, P and Si) in the lower Mekong River

Summary Changing human land use is accelerating global element cycling and appreciably altering ecosystems in the riverine–estuarine systems. This is evident by dramatic shifts in the supply of nutrients (C, N, P, Si). However, very little is known about the magnitude and rates of these changes. We examine the Mekong, one of the world largest rivers, to assess on a whole-of-system scale, the spatial, monthly and inter-annual flux of nutrients and stoichiometric ratios using a huge data-set (1985–2011). Seasonal and spatial patterns are apparent and linked to hydrology. The estimated mean flux (×109 mol/y) of elements from the Mekong at Pakse are 414.5 for DIC, 4.1 for DIN (3.3 for NO3−-N and 0.8 for NH4+-N), 10.2 for TN, 0.32 for DIP, 0.46 for TP and 62.8 for DSi, respectively, which are intermediate relative to other large rivers. However, compared to the river reach at Pakse, the total river fluxes are two-fold greater for C, N, P and DSi. Annual flux increases significantly for DIC, NO3−-N, DIN, TN and DSi, and is especially pronounced for all N and P species during the recent decade (1998 onward). Distinct shifts of nutrient stoichiometry, with far-reaching changes for phytoplankton productivity in the Mekong estuary are also evident, as the system shifts from potentially N limited to P limited. These notable changes to the exports and ratios of nutrient variables and anthropogenically-driven nutrient concerns are becoming a defining feature of the Mekong Plume to the South China Sea.

Photosynthesis and early Earth

Life has been built on the evolution and innovation of microbial metabolisms. Even with our scant understanding of the full diversity of microbial life, it is clear that microbes have become integral components of the biogeochemical cycles that drive our planet. The antiquity of life further suggests that various microbial metabolisms have been core and essential to global elemental cycling for a majority of Earth's history.

Direct and Indirect Effects of Estuarine Reclamation on Nutrient and Metal Fluxes in the Global Coastal Zone

We demonstrate that land reclamation in estuaries is resulting in very large-scale loss of intertidal area and disconnection of stored sediment with the water column. This process is not just causing loss of estuarine ecosystem services, it is also having a major deleterious impact on the ability of estuaries to retain nutrients and trace metals. The global scale of loss of estuarine wetlands and subtidal sediments has reached the point where the impact of this loss of estuarine retention is likely to be affecting coastal seas worldwide and possibly global element cycles.

Proteomik-Werkzeuge für Mikroorganismen

Microorganisms play central roles in global elemental cycles and ecosystem functioning. The molecular basis and mechanisms of the various ecophysiological capacities of environmental microbes are, however, often unknown or not clearly understood. In this regard, proteomic approaches promise plenty of opportunities. This short note recapitulates state-of-the-art proteomic tools for environmental microbiology and presents selected research examples.

Reconsidering the role of carbonate ion concentration in calcification by marine organisms

Abstract. Marine organisms precipitate 0.5–2.0 Gt of carbon as calcium carbonate (CaCO3) every year with a profound impact on global biogeochemical element cycles. Biotic calcification relies on calcium ions (Ca2+) and usually on bicarbonate ions (HCO3−) as CaCO3 substrates and can be inhibited by high proton (H+) concentrations. The seawater concentration of carbonate ions (CO32−) and the CO32−-dependent CaCO3 saturation state (ΩCaCO3) seem to be irrelevant in this production process. Nevertheless, calcification rates and the success of calcifying organisms in the oceans often correlate surprisingly well with these two carbonate system parameters. This study addresses this dilemma through the rearrangement of carbonate system equations which revealed an important proportionality between [CO32−] or ΩCaCO3and the ratio of [HCO3−] to [H+]. Due to this proportionality, calcification rates will always correlate as well with [HCO3−] / [H+] as they do with [CO32−] or ΩCaCO3 when temperature, salinity, and pressure are constant. Hence, [CO32−] and ΩCaCO3 may simply be very good proxies for the control by [HCO3−] / [H+], where [HCO3−] serves as the inorganic carbon substrate and [H+] functions as a calcification inhibitor. If the "substrate–inhibitor ratio" (i.e., [HCO3−] / [H+]) rather than [CO32−] or ΩCaCO3 controls biotic CaCO3 formation, then some of the most common paradigms in ocean acidification research need to be reviewed. For example, the absence of a latitudinal gradient in [HCO3−] / [H+] in contrast to [CO32−] and ΩCaCO3 could modify the common assumption that high latitudes are affected most severely by ocean acidification.

English

Ocean acidification (OA) research seeks to understand how marine ecosystems and global elemental cycles will respond to changes in seawater carbonate chemistry in combination with other environmental perturbations such as warming, eutrophication, and deoxygenation. Here, we discuss the effectiveness and limitations of current research approaches used to address this goal. A diverse combination of approaches is essential to decipher the consequences of OA to marine organisms, communities, and ecosystems. Consequently, the benefits and limitations of each approach must be considered carefully. Major research challenges involve experimentally addressing the effects of OA in the context of large natural variability in seawater carbonate system parameters and other interactive variables, integrating the results from different research approaches, and scaling results across different temporal and spatial scales.

Catabolic rates, population sizes and doubling/replacement times of microorganisms in natural settings

Directly assessing the impact of subsurface microbial activity on global element cycles is complicated by the inaccessibility of most deep biospheres and the difficulty of growing representative cultivars in the laboratory. In order to constrain the rates of biogeochemical processes in such settings, a quantitative relationship between rates of microbial catalysis, energy supply and demand and population size has been developed that complements the limited biogeochemical data describing subsurface environments. Within this formulation, rates of biomass change are determined as a function of the proportion of catabolic power that is converted into anabolism—either new microorganisms or the replacement of existing cell components—and the amount of energy that is required to synthesize biomass. Catabolic power is related to biomass through an energy-based yield coefficient that takes into account the constraints that different environments impose on biomolecule synthesis; this method is compared to other approaches for determining yield coefficients. Furthermore, so-called microbial maintenance energies that have been reported in the literature, which span many orders of magnitude, are reviewed. The equations developed in this study are used to demonstrate the interrelatedness of catabolic reaction rates, Gibbs energy of reaction, maintenance energy, biomass yield coefficients, microbial population sizes and doubling/replacement times. The number of microorganisms that can be supported by particular combinations of energy supply and demand is illustrated as a function of the catabolic rates in marine environments. Replacement/doubling times for various population sizes are shown as well. Finally, cell count and geochemical data describing two marine sedimentary environments in the South Pacific Gyre and the Peru Margin are used to constrain in situ metabolic and catabolic rates. The formulations developed in this study can be used to better define the limits and extent of life because they are valid for any metabolism under any set of conditions.

An Introduction to Marine Sediments with an Emphasis on Sediment Organic Matter Remineralization

SummaryThe processes occurring in the upper several meters of marine sediments have a profound effect on the local and global cycling of many elements. For example, the balance between organic carbon preservation and remineralization in sediments represents the key link between carbon cycling in active, surface reservoirs in the oceans, atmosphere, and on land, and carbon that cycles on much longer, geological time scales, i.e., in sedimentary rock, and in coal and petroleum deposits. Understanding processes occurring in surficial marine sediment is also important in the accurate interpretation of paleoceanographic sediment records, since sediment processes can sometimes significantly alter the primary “depositional” signal recorded in the sediments. In coastal and estuarine sediments nitrogen and phosphorus remineralization in the sediments can provide a significant fraction of the nutrients required by primary producers in the water column. Similarly, in coastal and estuarine sediments subjected to elevated anthropogenic inputs of certain toxic metals, sediment processes affect the extent to which these sediments represent “permanent” versus “temporary” sinks for these metals.The geochemistry of marine sediments is controlled by both the composition of the material initially deposited in the sediments and the chemical, biological or physical processes that affect this material after its deposition. These processes fall within the general category of what is commonly referred to as early diagenesis. One very crucial aspect of the study of early diagenesis in marine sediments is that the oxidation, or remineralization, of organic matter deposited in the sediments is either the direct or indirect causative agent for many of these early diagenetic changes. Given this pivotal role that organic matter remineralization plays in many early diagenetic processes, significant efforts have gone into understanding and quantifying these processes.This lecture provides a brief introduction to marine sediment geochemistry focusing on the basic controls on organic matter remineralization in sediments. It is based on a lecture I recently gave to an undergraduate geology class in stratigraphy. I believe that it could also be useful in an undergraduate class in general oceanography, low temperature geochemistry or environmental geochemistry.Lecture summaryThe geochemistry of marine sediments is controlled by both the composition of the material initially deposited in the sediments and the chemical, biological or physical processes that affect this material after its deposition. These processes fall within the general category of what is commonly referred to as early diagenesis. One key aspect of the study of early diagenesis in marine sediments is that the oxidation, or remineralization, of sediment organic matter is either the direct or indirect causative agent for many early diagenetic changes.Given the pivotal role that organic matter remineralization plays in early diagenetic processes, significant efforts have gone into understanding and quantifying these processes. This lecture provides a brief introduction to marine sediment geochemistry, focusing on the basic controls of organic matter remineralization in sediments. I believe that the lecture could be useful in an undergraduate class in general oceanography, low temperature geochemistry or environmental geochemistry. It could also be useful in introductory graduate classes in these latter two areas.

Metallophores and Trace Metal Biogeochemistry

Trace metal limitation not only affects the biological function of organisms, but also the health of ecosystems and the global cycling of elements. The enzymatic machinery of microbes helps to drive critical biogeochemical cycles at the macroscale, and in many cases, the function of metalloenzyme-mediated processes may be limited by the scarcity of essential trace metals. In response to these nutrient limitations, some organisms employ a strategy of exuding metallophores, biogenic ligands that facilitate the uptake of metal ions. For example, bacterial, fungal, and graminaceous plant species are known to use Fe(III)-binding siderophores for nutrient acquisition, providing the best known and most thoroughly studied example of metallophores. However, recent breakthroughs have suggested or established the role of metallophores in the uptake of several other metallic nutrients. Furthermore, these metallophores may influence environmental trace metal fate and transport beyond nutrient acquisition. These discoveries have resulted in a deeper understanding of trace metal geochemistry and its relationship to the cycling of carbon and nitrogen in natural systems. In this review, we provide an overview of the current state of knowledge on the biogeochemistry of metallophores in trace metal acquisition, and explore established and potential metallophore systems.